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Publication numberUS3227552 A
Publication typeGrant
Publication dateJan 4, 1966
Filing dateAug 27, 1964
Priority dateMay 13, 1960
Also published asDE1167655B
Publication numberUS 3227552 A, US 3227552A, US-A-3227552, US3227552 A, US3227552A
InventorsKeith E Whitmore
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Preparation of photographic direct positive color images
US 3227552 A
Abstract  available in
Images(1)
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Claims  available in
Description  (OCR text may contain errors)

Jan. 4, 1966 w o 3,227,552

PREPARATION OF PHOTOGRAPHIC DIRECT POSITIVE COLOR IMAGES Filed Aug. 27, 1964 TOPCOA T LA YER LIGHT-SENSITIVE EMULSION LAYER CONTAIN/N6 DYE -F ORMl/VG COUPLER SUPPORT SUPP OR T MO/PDA/VT LAYER RUPTURAEL E POO C ON TA lNl/VG L PROC E .5 SM! 6 C OMPOS/ T/ ON TOPCOAT LAYER BLUE-SENSITIVE EMULSION LAYER CONTAIN/N6 YELLOW DYE -E ORM/NC COUPLER INTERLAYER GREEN-SENSITIVE EMULSION LAYER CONTAIN/N6 MAGENTA DYE -FORM/N6 COUPLER //VTERLA YER REO-SENS/T/VE EMULS/ON LAYER CONTAIN/N6 CYA/V DYE-FORMl/VG COUPLER 2O SUPPORT FIG. 2

KEITH E WH/TMORE INVENT R.

United States Patent 3,227,552 PREPARATION OF PHOTOGRAPHIC DIRECT POSITIVE COLOR IMAGES Keith E. Whitmore, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Aug. 27, 1964, Ser. No. 392,471 31 Claims. (Cl. 963) This application is a continuation-in-part application of my copending application Serial No. 220,028 filed August 28, 1962, now abandoned, which in turn is a continuationin-part application of Serial No. 29,075 filed May 13 1960, now abandoned.

The present invention concerns color photography, and more particularly, photographic silver halide emulsions suitable for use in preparing direct positive color images and methods for processing such emulsions.

There are several direct positive or reversal color processes known in the art, including processes for preparing positive color transparencies and processes for preparing positive images by diffusion of dyes produced on development to a receiving sheet. Good color saturation or dye density is desired in such color processes. It is particularly desirable in color diffusion transfer processes that the emulsion layers be relatively thin to aid in the reduction of the image transfer time. However, the emulsion layers must be of sufficient thickness to contain enough color coupling material to form transfer images having high color density.

It is an object of this invention to provide novel photographic silver halide emulsions that substantially improves the efliciency of processes for preparing positive color images when used in such processes.

It is another object of this invention to provide new photographic silver halide emulsions that result in increased color saturation When developed with photographic aromatic primary amino color developing agents.

It is another object of this invention to provide a new process for preparing direct positive color images having increased dye density.

it is likewise an object of this invention to provide a new process for preparing direct positive color images having decreased dye density in the D area, to wit, irn proved clean out.

It is still another object of this invention to provide a new photographic reversal color process.

It is also an object of this invention to provide a new diffusion transfer process for preparing positive color images having improved dye density.

These and other objects of this invention are attained by means of this invention as described hereafter with particular reference to certain preferred embodiments.

The invention includes color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent photographic elements that contain at least one reversal silver halide emulsion wherein the silver halide forms latent images predominantly inside the silver halide grains when exposed to light. A photographic color coupling material that forms a dye in the regions of development with oxidation product of the color developing agent is positioned contiguous to the silver halide of the emulsion. The color development is carried out in the presence of a hydrazide or a hydrazone as described below to form a direct positive dye image, the hydrazide or hydrazone not comprising the dye image formed. Sulfonated hydroquinones as described below are also useful addenda.

The reversal or direct-positive silver halide emulsions utilized in the photographic or light-sensitive elements of the invention are to be distinguished from emulsions containing silver halide grains that have substantial surface 3,227,552 Patented Jan. 4, 1966 sensitivity and form latent images when exposed to light on the surface thereof. Suitable silver halides include silver bromide, silver bromoiodide, silver chloroiodide, and silver chlorobromoiodide. For a description of suitable emulsions that form latent images internal to the silver halide grains, reference is made to Davey et 21., US. Patent 2,592,250; and Glafkides, Photographic Chemistry, Volume 1, pages 31-2, Fountain Press, London. Typically such emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1 10 and 1 second, bleaching 5 minutes in a 0.3% potassium ferricyanide solution at F. and developing for about 5 minutes at 65 F. in Developer B below (an internal-type developer), have a sensitivity, measured at a density of 0.1 above fog, greater than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in Developer A below (a surface-type developer).

DEVELOPER A Water to make 1 liter.

In preparing the silver halide emulsions used in layers on the photographic elements of the invention, a wide variety of hydrophilic organic colloids can be utilized as the vehicle or carrier. It is preferred to utilize gelatin as the hydrophilic colloid or carrier material although such material as polyvinyl alcohol and its water-soluble derivatives and copolymers, water-soluble c-opolymers such as polyacrylamide, imm-idized polyacrylamide, etc.,

and other water-soluble film-forming materials that form.

water-permeable coats such as colloidal albumin, watersoluble cellulose derivatives, etc., can be utilized in preparing the present photographic elements. Compatible mixtures of two or more of such colloids can also be utilized.

A wide variety of hydrazides and hydrazones can be utilized in practicing the present invention. hydrazides and hydrazones are nitrogen-containing compounds having the formulas wherein R is an aryl radical and including substituted aryl radicals; R is an acyl or a sulfonyl radical; and R is an alkylidene radical and including substituted alkylidene radicals. Typical aryl radicals for the substituent R have the formula XR wherein R is an aryl radical and X can be such substituent-s as hydrogen, hydroxy, amino, alkyl, alkylamino, arylamino, heterocyclic amino (amino contains a heterocyclic moiety), alkoxy, aryloxy, acyloxy, arylcarbonamido, alkylcarbonamido, heterocyclic carbonamido (earbonamido contains a heterocyclic moiety),

arylsulfonamido, alkysulfonamido, sulfonamido (sulfonamido contains and heterocyclic a heterocyclic Suitable moiety). Typical acyl and sulfonyl radicals for the substituent R have the formula wherein Y can be such substituents as alkyl, aryl and heterocyclic radicals. Z can represent a hydrogen atom or the same substituents as Y as well as radicals having the formula iOA to form oxalyl radicals wherein A is an alkyl, aryl or a heterOcycl-ic radical. Typical alkylidene radicals for the substituent R have the formula =CHD wherein D can be a hydrogen atom or such radicals as alkyl, aryl and heterocyclic radicals. Typical aryl substituents for the above-described hydrazides and hydrazones include phenyl, naphthyl, diphenyl, and the like. Typical heterocyclic substituents for the above-described hydrazides and hydrazones include azoles, azines, furyl, th-iophene, quinoline, pyrazole, and the like. Typical alkyl (or alkylene) substituents for the above-described hydrazides and hydrazones have 1 to 22 carbon atoms including methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, t-butyl, amyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, n-eicosyl, ndocosyl, etc.

Illustrative specific hydrazides and hydrazones used in the invention include:

1-acetyI-Z-phenylhydrazide 1-acetyl-2- 4-hydroxyphenyl hydrazide l-acetyl-2- 4-aminophenyl hydrazide l-ace tyl-2- 4-methylphen yl hydrazide l-acetyl-Z- (4-acetan1idophenyl hydrazide l-acetyl-2- 4-benzamid ophenyl hydrazide 1-acetyl-2- 4-methoxyphenyl) hydrazide (8) 1-acetyl-2- [4- 3-sulfobenzamido) phenyl] hydrazide (9) 1-acetyl-2-(4-phenylsulfamidophenyl)hydrazide 10) l-acetyl-Z- 4-methylsulfonamidophenyl hydrazide 11) 1-phenylsulfonyl-2-phenylhydrazide (12) 1-methylsulfonyl-2-phenylhydrazide l3) l-benzoyl-2-phenylhydrazide 14) 1-benzoyl-2- (4-benzamidophenyl) hydrazide l5 lethoxalyl-Z-phenylhydrazide (16) l-methylsulfonyl-Z- 3-phenylsulfonamidophenyl) hydrazide 17) 1- 4-acetamidophenylsulfonyl -2-( l-naphthyl) hydrazide 18) l-ethylsulfonyl-Z- 4-diethylaminophenyl hydrazide 19) l-phenylsulfonyl-Z- (4-benzamido-2,S-diethoxyphenyl hydrazide (20) 5-(1-carb0-2-phenylhydrazino)1-pheny1-3- pyrazolidone (21) 2-(1-carbo-2-phenylhydrazino)furan (22) 4-( 1-carbo-2-phenylhydrazino pyridine (23) 2-( l-carbo-2-phenylhydrazino) benzothiazole (24) 1- 2- 2,4-di-tert-amylphenoxy) -5-( 3 ,5 -disulfobenzamido benzoyl -2-phenylhydrazide (25) 1-acetyl-2-{ 4- 2- 2,4-di-tert-amylphenoxy -5 3 ,5

disulfobenzamido) benzamido phenyl}hydrazide 26) 1-lauroyl Z-phenylhydrazide (27) l-lauroyl-2- [4- 3-sulfobenzamido) phenyl] hydrazide (28) l-methylsulfonyl-Z- 4-octadecylphenyl hydrazide (29) l-octadecyloXalyl-2-phenylhydrazide (3 O) l-octadecyloxalyl-Z- [4- (3 -sulfobenzamido) phenyl] hydrazide (31) l-lauroyl-Z- 4- (fi-methylsulfonamidoethyl) phenyl] hydrazide (3 2) 1- [3- 2,4-di-tert-amyl-X-sulfophenoxy) benzoyl] -2- phenylhydrazide (3 3) 5-{ l-carbo-Z- [4 a-sulfostearamido phenyl] hydrazino}-1-phenyl-3 -pyrazo1idone (34) Formaldehyde phenylhydrazone (35) Formaldehyde 4- (fi-methylsulfonamidoethyl) phenylhydrazone (36) Mucochloric acid 4-(B-methylsulfonamidoethyl)- phenylhydrazone (37) Acetone 4-methylphenylhydrazone (38) Benzaldehyde 4-(ii-methylsulfonamidoethyl) phenyl hydrazone (39) Benzaldehyde 4-methoxyphenylhydraz0ne 40) Benzaldehyde 4- 3-sulfobenzamido phenylhydrazone (41) Formaldehyde 4-methylsulfonamidophenylhydrazone (42) Acetaldehyde 4-phenylsulfonamidophenylhydrazone (43) P-tolualdehyde 4-diethylaminophenylhydrazone (44) cinchoninaldehyde 4-acetamidophenylhydrazone (45) Z-furaldehyde 4-methylsulfonamido-l-naphthylhydrazone 46) Nicotinaldehyde 4- 3-methylsulfamylbenzamido 2,5-diethoxyphenylhydrazone 47) Hendecanal 4- a-sulfostearamido phenylhydrazone (48) 3-octadecyloxybenzaldehyde phenylhydrazone (49) 3-octadecyloxybenzaldehyde 4-(3-sulfobenzamido) phenylhydrazone (50) Benzaldehyde 4-[2-(2,4-di-tert-amylphenoxy)-5- 3,5 -disulfobenzamido) benzamido] phenylhydrazone dipotassiurn salt (51 Oxyguargum 4-(fi-methylsulfonamidoethyl) phenylhydrazone (52) 1-phenyl-acetyl-Z-phenylhydrazide (53) l-formyl-2-phenylhydrazide In accordance with the invention, the described hydrazidcs and hydrazones can be incorporated in the present color coupler-containing silver halide emulsions, in the color developing composition containnig the aromatic primary amino color developing agent, or in receiving layers or sheets in embodiments wherein the present color emulsions are developed in contact with a receiving layer or sheet and diffusible dyes are transferred to such layers or sheets.

The amount of hydrazide or hydrazone utilized can be Widely varied, substantial amounts of such addenda not being objectionable. The examples below illustrate the use of varying concentrations of such addenda for use in emulsions, developers and receiving layers. One skilled in the art could readily determine optimum concentrations for a particular color system. Generally I utilize between about 1 to 20 mg. of hydrazide or hydrazone addenda per square foot of each light-sensitive layer of the photoelement, or an equivalent amount in the receiving sheet, or about .1 to 2 grams of hydrazide or hydrazone addenda per liter of developer. However, larger or smaller amounts are suitable.

Particularly useful photographic elements of the invention are those containing on the emulsion side of the support a substituted hydroquinone containing at least one sulfonic acid radical (SO H), including ammonium and alkali metal salts thereof. Such sulfonated hydroquinones cooperate with the above-described hydrazides and hydrazones to give increased color or dye yield, to wit, increased color D Particularly useful sulfonated hydroquinones of the invention have the formulas OH OH i i R5 NH( i R or iNHR can be substituted, R and R for example suitably being aryl radicals such as phenyl and alkyl radicals as well as hydrogen atoms and sulfonic acid radicals. The alkyl radicals can be substituted alkyl radicals and include aralkyl radicals. The chain length or size of the alkyl, alkyleen and acylamino radicals can be widely varied depending on the degree of diffusibility desired, one skilled in the art readily being able to ascertain the amount of ballasting needed for a particular purpose. Alkyl and alkylene radicals having 1 to 22 carbon atoms are suitable,

although alkyl radicals having 8 to 22 carbon atoms and alkylene radicals having 1 to 8 carbon atoms are preferred.

Illustrative sulfonated hydroquinones used in the photographic elements of the invention include:

( 1 2-{13-{3- 3-(4-amyl-x-sulfophenoxy) -benzamido] benzamido}-ethyl}-hydroquinone (sodium salt) (2) 2,5-bis{N-{3-[2,4-(diamylphenoxy)-5-(2-sulfobenzamido) -b enzamido] -phenyl}-carbamylmethyl}-hydroquinone (sodium salt) (3) S-octadecyl-Z-(2-sulfo-tert.-butyl)hydroquinone (sodium salt) (4) 5-sec.-octadecyl-2-(2-sulfo-tert.-butyl)hydroquinone (sodium salt) (5) 2,5 -bis{5- 3-(p-tert.-amylphenoxy) -x-sulfo] benzamidoethyl}hydroquinone (sodium salt) (6) 2- [2- (2,4"-di-tert.-amylphenoxy) -5 3",5-disulfobenzamido)-benzamido] -hydroquinone (sodium salt) (7) Potassium sec.-undecyl-hydroquinone-X-sulfonate (8) Potassium n-hexadecyl-hydroquinone-x-sulfonate (9) Potassium n-octadecyl-hydroquinone-x-sulfonate 10) Potassium 2-methyl-5-sec.-octadecyl-hydroquinonex-sulfonate 1 l Potassium-3 -benzyl-x-sulfonate (l2) Potassium-3-p-ethylbenzyl-x-sulfonate 13 Potassium-3- (p-benzyl -benzyl-X-sulfonate The above-described sulfonated hydroquinones can be incorporated directly in the silver halide emulsion layers,

in interlayers or in overcoat layers comprising the photographic elements of the invention. Optimum concentrations can be determined by one skilled in the art although I generally utilized about .1 to 10 mg, and preferably about .1 to 5 mg, of the sulfonated hydroquinone per square foot of each light-sensitive layer of the photoelement. However, larger or smaller amounts are suitable.

The photographic elements of the invention have incorporated contiguous to the silver halide grains of at least one silver halide emulsion layer a nondifiusible photographic color coupler that reacts with oxidized aromatic primary amino color developing agent to form a dye. The couplers can be in the silver halide emulsion layer or in an adjacent layer. Suitable couplers are well known in the art and are generally 5-pyrazolone, phenolic or open-chain ketomethylene compounds. For convenience of reference, nondiffusible couplers that form diffusible dyes on color development are referred to herein as DDR or dilfusible dye-releasing couplers. DDR couplers are useful in preparing direct positive color diffusion transfer images in accordance with the invention. Nondiffusible couplers that form nondilfusible dyes on color development can also be utilized to prepare direct positive images in accordance with the invention.

The DDR couplers are used in preparing photographic elements of the invention having utility in diffusion transfer processes, such couplers including those having the formulas DYE-LINK(COUP--BALL) and BALL-LINK( COUPSOL) n a wise to a reception layer.

wherein: I I (1) DYE is a dye radical containing an acidic solubilizing radical;

(2) LINK is a connecting or linkage radical such as azo (N N) azoxy 0 (-N= mercury (Hg), oxy (-O), alkylidene (includes both a e \I I 0 and =0 wherein R is a hydrogen atom or an alkyl radical generally having 1 to 4 carbon atoms), monothio (3) COUP is a photographic color coupler radical such as a S-pyrazolone coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, the coupler radical being substituted in the coupling position with the connecting or linkage radical;

(4) BALL is a photographically inert organic radical of such molecular size and configuration as to render the coupler nondilfusing in the element in the alkaline processing solution;

(5) SOL is either a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing radical, SOL always being an acidic solubilizing radical when the color developing agent is free of an acidic solubilizing group; and

(6) n is an integer of l or 2 when LINK is an alkylidene radical, and n is always 1 when LINK is one of the other aforementioned connecting radicals, namely, azo, azoxy, mercuri, oxy, monothio, or dithio.

The acidic solubilizing radicals attached to the diffusible dye-releasing (DDR) couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes ditfusible in the element in alkaline processing solutions. Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamido, and hydroxy-substituted groups that lend to dyes negative charges. Typical dye radical substituents (DYE) of the DDR couplers include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum. The dye radicals contain acidic solubilizin g moieties.

When DDR couplers having the formula DYE- LINK(COUP-BALL) as described above are reacted With oxidized color developing agent, the connecting radical (LINK) is split and a diifusible preformed acid dye (DYE) is released which diffuses image- An acidic solubilizing group on the preformed dye lends ditfusibility and m'ordantability to the dye molecule. The coupling portion of the DDR coupler (COUP) couples with color developing agent oxidation product to form a dye that is nonditfusible in the element because of the attached ballasting group (BALL) in a noncoupling position. In this type of DDR coupler, the color of the dilfusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the diffusible image.

When DDR couplers having the formula BALL LINK-(COUPSOL) as described above are reacted with oxidized color developing agent, the connecting radical (LINK) is split and a difi'usible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the DDR coupled which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion' 7 (COUP) of the DDR coupler or to the color developing agent. The ballast portion of the DDR coupler remains immobile. In this type of DDR coupler, the color of the ditfusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).

When the coupler radical (COUP) in the DDR couplers is a S-pyrazolone radical, it is preferred to have substituted in the 3-position of the pyrazolone moiety and anilino group or an alkoxy group. When the coupler radical (COUP) in the DDR couplers is a cyanforming phenolic coupler radical, I prefer to have substituted in the ortho or 2-position of the phenolic moiety a fully substituted amido group (e.g.,

Rlfl COAT--12 wherein R is an alkyl group or a phenyl group). Also, when the connecting radical (LINK) in the DDR couplers having the formula, BALLLINK--(COUP SOL) is an azo radical, it is preferred that the ballasting radical (BALL) be a phenyl redaical containing either a hydroxy group or an amino group (--NH substituted in the ortho or 2-position of the phenyl moiety.

The nature of the ballast groups (BALL) in the DDR coupler compounds described above is not critical as long as they confer nondiifusibility to the coupler compounds. Typical ballast groups exemplified hereinafter in the specific couplers disclosed include long chain alkyl radicals or several short chain alkyl radicals having e.g., 8 to 22 carbon atoms, linked directly or indirectly to the coupler molecules as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound. Useful ballast groups generally have at least 8 carbon atoms.

DDR couplers are known in the art. Typically suitable DDR couplers and methods for preparing such couplers are described in copending application Serial No. 222,105 filed September 7, 1962 and in the following patents: Canadian Patents 602,606 and 602,607; British Patents 840,731 and 904,364; French Patents 1,224,012, 1,291,110 and 1,293,709; and Belgian Patents 578,470, 591,444, 603,213, 603,747 and 625,137.

Likewise, nondiffusible couplers that form nondiffusible dyes on color development are well-known in the art. Typical of such couplers are disclosed in the following patents: U.S. Patent 2,956,876 (column 5, lines 30 to 59); U.S. Patent 2,640,776; U.S. Patent 2,407,210 and U.S. Patent 2,474,293.

The coupling position of the above-described couplers is well known to those skilled in the art, this being the position on the coupler molecule that reacts or couplers with oxidized color developing agent. Phenolic couplers, including a-naphthols, couple at the 4-position, open-chain ketomethylene couplers couple at the carbon atom forming the methylene moiety (e.g.,

*denoting the coupling position), and S-pyrazolone couplers couple at the carbon atom in the 4-position.

The terms nondiifusing and nondiffusible used herein as applied to couplers and dyes have the meaning commonly applied to the term in color photography and denoate materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention in the presence of aqueous alkaline processing compositions. The terms diffusing and diffusible as applied to the dyes released from the DDR couplers in the present processes and the developing agents have the converse meaning and denote materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of aqueous alkaline processing compositions.

The photographic elements of the invention are processed with alkaline compositions in the presence of an aromatic primary amino color developing agent, p-phenylenediamine developing agents being particularly useful. The color developing agent can be either incorporated in an aqueous alkaline composition that is applied to the present photographic elements on processing or the color developing agent can be incorporated in the lightsensitive element. Typical aromatic primary amino color developing agents include:

N,N-diethyl-p-phenylene diamine, 2-amino-5-diethylamino toluene, N-ethyl-B-methanesulfonamido-ethyl-3 -methyl-4-aminoaniline, 4-amino-N-ethyl-3 -methyl-N- (fi-sulfoethyl aniline, 4-amino-N-ethyl-3-methoxy-N- (fl-sulfoethyl) aniline, 4-amino-N-ethyl-N- (fi-hydroxyethyl) aniline, 4-amino-N,N-diethyl-3-hydroxymethyl aniline, 4-amino-N-methyl-N- B-carboxyethyl) aniline, 4-amino-N,N-bis (fi-hydroxyethyl) aniline, 4-amino-N,N-bis B-hydroxyethyl) -3 -methyl aniline, 3 -acetarnido-4-amino-N,N-bis fi-hydroxyethyl) aniline, 4-amino-N-ethyl-N- 2,3 -dihydroxypropyl -3 -methyl aniline sulfate salt, 4-amino-N,N-diethyl-3- S-hydroxypropoxy) aniline,

the like.

When the color developing agent is used in the present photographic elements, it is advantageous to use forms that have substantial stability in emulsions such as Schiff base derivatives of primary amino developing agents. Such Schifi bases are prepared by reacting primary amino developing agents with sulfonated, hydroxylated or carboxylated aromatic aldehydes of the benzene or naphthalene series. A typical Schiff base color developing agent can be prepared by reacting 2-amino-5-diethylaminotoluene and o-sulfobenzaldehyde. Other Schiif base developers that are useful as such, as salts or as sulfur dioxide complexes include:

N ethyl N-(ti-hydroxyethyl)-4-(o-sulfobenzylideneamino)aniline sodium salt,

N,N diethyl 4-(2,4-dihydroxybenzylideneamino)-3 methylaniline,

N ethyl S-methyl-N-(B-methylsulfonamidoethyl)-4-(2- sulfobenzylideneamino)aniline sodium salt,

and the like.

Such incorporated developing agents can be activated by immersing the photographic element in an aqueous alkaline solution or by spreading an aqueous alkaline solution on the surface of the element. Such incorporated developing agents can be positioned in any layer of the present photographic elements from which the developing agents can be readily made available for development on activation with aqueous alkaline solutions. Generally, such incorporated color developing agents are incorporated in layers contiguous to the light-sensitive silver halide emulsion layers, although the color developing agent can be utilized in the silver halide emulsion layers.

The reception layer used to receive the diffused dye images on color development when DDR couplers are used in the photoelements of the invention can be either a separate receiving sheet pressed in contact with the photoelement or a layer integral with the photoelement.

When the reception layer is a separate reception sheet, the development and transfer operations can be effected by bathing either or both the exposed photographic element and the mordanted reception sheet in the developing solution before rolling into contact with each other. Alternatively, a viscous developing composition can be placed between the elements for spreading in a predetermined and amount across and in contact with the exposed surface of the sensitive element so as to provide all of the solution required for the picture area. The viscous developing composition is desirably utilized in one or more pods or containers integral with the photographic element or the reception sheet that can be readily ruptured when development is desired, suitable viscous developer utilization techniques being disclosed in U.S. Patents 2,543,181; 2,559,643; 2,647,049; 2,647,056; 2,661,293; 2,698,244; 2,698,798; and 2,774,668. Such processing techniques utilizing viscous processing compositions and rupturable pods can also be used to color develop photographic elements containing couplers that form nondiffusible dyes.

When the reception layer for receiving the difiusible dye is an integral part of the photosensitive assembly, it is also useful. A typical element of this type can comprise a support, a mordanted colloid layer thereon and the various emulsion layers described above coated thereover. When easily dissolved emulsions are used such as those containing polyvinyl alcohol or alkali-soluble cellulose ether phthalate vehicles, or a wet or dry stripping layer containing such vehicles is provided between the emulsions and reception layer, the developed emulsion layers can then be readily separated from the reception layer leaving the dye image thereon. Similarly, the reception layer can be initially bonded to the outer emulsion surface. In this case, it is preferred to expose through the support of the senistive element unless the reception layer itself is transparent. Such photoelements can be processed in the same manner as those not containing integral reception layers.

The dye reception layers used in the invention can contain any of the conventional mordant materials for dyes. The reception layer can contain mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone described in U.S. Patent 2,882,156. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in U.S. Patent 2,484,430 and cetyl trirnethylammonium bromide, etc. Particularly effective mordanting compositions are described in Belgian Patent 634,515. Typical of such mordanting compositions include at least one hydrophilic organic colloid containing a finely-divided, uniform dispersion of droplets or globules of a high-boiling, waterirnrniscible organic solvent in which is dissolved a high concentration of a cationic, nonpolymeric, organic dyemordanting compound for acid dyes. Other mordanting compositions described in Belgian Patent 634,515 include at least one hydrophilic organic colloid containing a finelydivided, uniform dispersion of particles of a salt of an organic acidic composition containing free acid moieties and a cationic, non-polymeric, organic dye-mordanting compound for acid dyes. Furthermore, the reception layer or sheet can be sufficient by itself to mordant the dye as in the case of the use of a sheet or layer of a polyamide or related polymeric material. Receiving sheets that release acidic material at a controlled rate such as are described in U.S. Patent 2,584,030 are useful.

Color developed photographic elements of the invention containing nondiffusible dye images on the support are treated after color development to remove silver in developed areas and to stabilize or fix silver halide in undeveloped areas. The silver in the developed areas can be bleached from the element by any of the conventional techniques used in color photography such as with aqueous baths containing water-soluble ferricyanides, dichromates or the like bleach bath components. Likewise, the silver halide in the undeveloped areas can be stabilized or fixed by any of the conventional techniques used in silver halide photography including the use of aqueous baths containing silver halide solvents such as Water soluble thiosulfates and thiocyanates. Also, monobath compositions that can be utilized to both bleach and fix color developed photographic elements are useful.

Typical suitable bleach-fix, or so-called blix baths, are

10 disclosed in German Patent 866,605 and British Patents 746,567 and 933,008. Such blix baths contain as bleaching agents a complex salt of an alkali metal and trivalent iron with an organic acid having the formula radical, R to R being substituted or unsubstituted hydrocarbon residues and R also suitably being a hydrogen atom. Such blix baths also contain known silver halide solvents such as water-soluble thiocyanates and thiosulfates. In addition, such blix baths can contain watersoluble polyethylene oxides, or Water-soluble polyalkylene oxides wherein some of the oxygen atoms are replaced by sulfur atoms. addenda have the formula Xl )m( )n( )m] wherein: R to R are bivalent organic radicals having 2 to 10 carbon atoms; In is an integer of 0 to n and p are integers of 1 to 100; Y is a radical having the formula -S, -4S

or mixtures thereof, R being a lower aliphatic radical having 1 to 3 carbon atoms; and X is a hydrogen atom or an aliphatic radical which can contain a substituent for improving the solubility of the compound (e.g., by hydroxyl, nitrile, amino, carboxylic acid or sulfonic acid groups or by a group of an acid of phosphorus). X can also be an acyl radical derived from an aliphatic monoor dicarboxylic acid.

In preparing the photographic elements of the invention, silver halide emulsions are preferably coated on photographic supports in the form of multilayer color photographic elements wherein at least three emulsion layers sensitive to different regions of the visible spectrum are coated on the support. For example, the uppermost light-sensitive emulsion layer is generally selectively sensitive to blue light, the next light-sensitive emulsion layer is generally selectively sensitive to green light, and the lightsensitive emulsion layer nearest the support is generally selectively sensitive to red light. Between the blue and green sensitive emulsion layers there is typically disposed a Carey Lea filter layer for absorbing blue radiation that may be transmitted through the uppermost blue sensitive layer. The red, green and blue light-sensitive silver halide layers have contiguous to the silver halide a cyanforming, a magenta-forming and a yellow-forming coupler respectively, so that dyes substantially complementary to the color sensitivities or color of light recorded in the silver halide emulsions are formed on color development. However, the physical disposition of the red, green and blue light-sensitive silver halide layers within the present photographic elements can be widely varied in accordance with usual practice. Such multilayer photographic elements can also have other interlayers or sublayers for specialized purposes in accordance with usual practice;

Typical of such sulfur-containing blix Nondilfusing couplers that form nondiffusing dyes on reaction with oxidized color developing agents are desirably incorporated in interlayers of photographic elements of the invention used to prepare diffusion transfer multicolor images, such couplers serving to improve color separation by scavenging oxidized color developing agent that wanders out of the silver halide emulsion layer in which it was generated.

Reflection prints as well as transparencies can be prepared with photographic elements of the invention that contain couplers that form nondiffusible dyes on color development, white pigmented supports for the emulsion layers being suitably used for preparing reflection prints and transparent supports being suitably used for preparing transparencies.

In another embodiment of the invention, a single layer light-sensitive element could be utilized to prepare fullcolor images. Three types of packets of differently sensitized silver halide emulsions and their corresponding couplers for subtractive color photography can be incorporated into a single emulsion layer on a photographic support. Reference is made to Godowsky US. Patent 2,698,794 for suitable methods for preparing silver halidecolor coupler packets.

The photographic elements of the invention are useful for color-proofing a set of half-tone silver separation positives of the type commonly employed in the printing industry before making the final press plates. In such a proofing process, three single color photographic elements containing silver halide that forms latent images inside the silver halide grains as described above can be typically employed wherein the elements contain nondifiusible couplers that form diifusible yellow, magenta and cyan dyes respectively when reacted with oxidized color developing agents. Such a proofing process is carried out by exposing each of the single-color photographic elements through a silver image separation positive of the photographic record substantially complementary to the color of the diffusible dye formed by reacting the couplers in the respective photographic elements with development oxidation product of an aromatic primary amino color developing agent. Each of the exposed elements is successively color developed in an aqueous alkaline color developing composition, and resulting dilfusible dyes successively transferred in register to a common recelving sheet for such dyes. In accordance with conventional dye transfer technique, the exposures and dye transfers are carried out with the aid of mechanical registration means such as pins, pegs or the like. The resulting three-color half-tone reproduction indicates the appearance of the final printed reproduction. Similarly, two color proofs can be prepared as Well as four-color proofs with photographic elements containing a coupler or more than one coupler that form diffusible black dyes on color development.

The drawings illustrate in section and in elevation typical photographic elements of the invention.

FIG. 1 of the drawings illustrates a typical single color photographic element of the invention wherein the dye-forming coupler is positioned in light-sensitive silver halide emulsion layer 11 coated on support 10. Over emulsion layer 11 is coated topcoat layer 12. Such an element is a singlecolor element and can be processed after exposure to prepare a direct positive color image by Wetting the exposed element with an aqueous processing solution containing an aromatic primary amino developing agent. If a DDR or diffusible dye-releasing coupler is used in emulsion layer 11, a receiving sheet having a reception layer which desirably contains a mordant is juxtaposed on topcoat layer 12 and the positive image formed when the DDR coupler reacts with oxidized color developing agent is allowed to diffuse and be transferred to the receiving sheet. If a coupler that forms a nondiffusible dye is used in emulsion layer 11, a dye image I 12 remains in layer 11 after color development which can thereafter be further processed to remove silver in exposed areas and silver halide in unexposed areas in the usual manner. The feature hydrazides or hydrazones, or the sulfonated hy-droquinones can be positioned in either or both layers 11 and 12.

FIG. 2 illustrates a typical multicolor photographic element of the invention as well as a typical mordanted receiving sheet and a rupturable pod containing a processing composition that can be suitably utilized in conjunction with such a photographic element. Coated on support 20 is red-sensitive emulsion layer 21 which contains a nonditfusible coupler that forms a cyan dye when reacted with oxidized color developing agent. Over redsensitive emulsion layer 21 is coated interlayer 22 that serves to separate green-sensitive emulsion layer 23 a nd red-sensitive emulsion layer 21. Interlayer 22 can contain such addenda as antioxidants, nondifi'usible couplers that react to form nonditfusible dyes with oxidized color developing agent from adjacent layers, filter dyes such as a magneta filter dye or the like. Green-sensitive emulsion layer 23 contains a nondiffusible coupler that forms a magneta dye on color development. Over green-sensitive emulsion layer 23 is coated interlayer 24 that serves to separate green-sensitive emulsion layer 23 and bluesensitive emulsion layer 25. Interlayer 24, like interlayer 22, can contain anti-oxidants, nondilfusible couplers that react to form nondiffusible dyes with oxidized color developing agent from adjacent layers, filter dyes and the like. Interlayer 24 typically contains yellow Carey Lea silver to serve as a filter for blue light. Blue-sensitive emulsion layer 25 contains a nondiffusible coupler that forms a yellow dye on reaction with oxidized color developing agent. Over blue-sensitive emulsion layer 25 is coated topcoat layer 26 that typically contains such addenda as antioxidants, ultraviolet absorbers and the like. The above-described sulfonated hydroquinones can be utilized in any of the layers 2146. In FIG. 2 is also illustrated a receiving sheet that can be used to receive dye images when DDR couplers are utilized in emulsion layers 21, 23 and 25. The receiving sheet comprises support 28 having coated thereon mordant layer 27 and affixed thereto rupturable pod 29 containing processing solution. Such processing solution is typically an aqueous alkaline material and can contain an aromatic primary amino color developing agent and a fogging agent if such are not incorporated in the light-sensitive element. Lightsensitive layers 21, 23 and 25 are direct positive silver halide emulsion layers wherein the silver halide grains have a substantial amount of sensitivity internal to the grains. When such emulsions are processed, they develop in positive image areas or unexposed areas. Accordingly, in the processing of an exposed photographic element of the type described in FIG. 2 of the drawings, development occurs in the unexposed areas and resulting oxidized color developing agent reacts with the color couplers in the respective red, green, and blue sensitive layers to form cyan, magenta, and yellow dyes respectively. A predominant proportion of the resulting oxidation product of the color developing agent is retained in the photographic element during the color development. In such subtractive color systems, coupler-s that form dyes that are substantially complementary to the color of light recorded in the silver halide contiguous to the couplers are more generally used. The feature hydrazides and hydrazones described above can be utilized in any layers 21-26 of the photographic element, in the alkaline processing composition of pod 29, or in mordant layer 27 of the receiving sheet.

The invention is ilustrated by the following examples of preferred embodiments thereof.

13 Example 1 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 square feet on a cellulose acetate film support:

(a) One mole of a silver chlorobromide photographic emulsion having high internal sensitivity and low surface sensitivity was prepared by the procedure described in Luckey et al., U.S. Patent 2,996,382 (Example 4 without fogging step), that was sensitized to red light,

(b) 590 grams of 10% gelatin in water solution,

(c) 360 cc. of 3% 2-(3,5-disulfobenzamido)-4-(3-octadecylcarbamylphenylthio)-5-methylphenol dipotassium salt in water solution (a cyan-forming coupler),

(d) 500 cc. of 15 saponin in water solution,

(6) cc. of 10% formaldehyde in water solution,

(f) 450 cc. of 2% 5-(1-carbo-2-phenylhydrazino)-1- phenyl-3-pyrazolidone in methanol solution, and

(g) Water to make a total of 7200 grams.

A similar color film was prepared except that the methenol solution of the hydrazide was omitted for purposes of comparison. The color films were then exposed for second with a 500 watt positive lamp and a 4.08 Corning filter on an Eastman Type 113 intensity scale sensitometer and thereafter developed in the viscous developer described below, Developer C.

DEVELOPER C Ascorbic acid g .4 4 amino-Nethyl-N-(fl-hydroxyethyl) aniline g 10.0 Benzotriazole g .3 Sodium hydroxide g 15.0 4% high viscosity carboxymethyl cellulose in aqueous solution cc 700.0

Water to make one liter.

The developing was carrier out by pressing the viscous developer between the color film samples and photographic image receiving sheets containing a cationic mordant at a thickness of .004 inch for 3 minutes at about 68 F. The color films were then separated from the receiving sheets leaving positive cyan images on the rerxziving sheets. The receiving sheet prepared from the color film containing the 5-(l-carbo-Z-phenylhydrazino)-1-phenyl-3-pyrazolidone had a positive cyan dye image having a substantially higher density than the receiving sheet prepared from the control color film containing no hydrazide as summarized by the data set out in Table A below.

TABLE A Emulsion addenda: Cyan D Control 1.13 5-(1-carbo-Z-phenylhydrazino) 1 phenyl-3-py- 'razolidone 1.50

The hydrazide emulsion addenda not only give improved dye density in accordance with the invention, but also particularly uniform transfers of diifusible dyes to receiving layers in diffusion transfer processes as described in Example 1. When related hydrazines such as phenyl hydrazine are utilized in the color developer, small bubbles form which result in nonuniform transfers of dyes to receiving sheets in diffusion transfer processes.

Example 2 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 sq. ft. on a cellulose acetate film support:

(a) One mole of a silver chlorobromoiodide emulsion having high internal sensitivity and low surface sensitivity was prepared by the procedure described in Davey et al., U.S. Patent 2,592,250, issued April 8, 1952,

(-b) 1070 grams of 10% gelatin in water solution,

(c) 2160 cc. of 5% 2-(3,S-disulfobenzamido)-4-(3-octa- A similar color film was prepared except that the methanol solution of 1-phenylacetyl-Z-phenylhydrazide was omitted for purposes of comparison. Samples of the color films were then exposed and processed as described in Example 1. The improved dye density resulting from the hydrazide addenda is summar zed by the data set out in Table B below.

TABLE B Emulsion addenda: Cyan D Control 0.23

1-phenylacetyl-2-phenylhydrazide 2.30

Example 3 A color film was prepared by coating the following photographic gelatine-silver halide emulsion over an area of 720 sq. ft. on a cellulose acetate film support:

(a) One mole of a silver chlorobromoiodide emulsion having high interial sensitivity and low surface sensitivity prepared by the procedure described in Davey et al., U.S. Patent 2,592,250, issued April 8, 1952,

(b) 1200 grams of 10% gelatin in water solution,

(c) 2160 cc. of 5% 2-(3,5-disulfobenzamido) 4-(3- octadecylcarbamylphenylthio) 5 methyl phenol dipotassium salt in water solution (a cyan-forming coupler),

(d) 500 cc. of 15% saponin water solution,

(e) 180 cc. of 2% n-octadecyl hydroquinone monosulfonate potassium salt in water solution,

(f) 9 cc. of 10% formaldehyde water solution,

(g) 150 cc. of 3% 1-lauroyl-Z-phenylhydrazide in methanol solution, and

(h) Water to make 7200 g.

A similar color film was prepared except that the 1-lauroyl-2-phenylhydrazide was omitted for purposes of comparison. Samples of the color films were then exposed and processed as described in Example 1. The improved dye density resulting from the hydrazide addenda is summarized by the data set out in Table C below.

TABLE c Hydrazide: Cyan D None 0.20 1-lauroyl-2-phenylhydrazide 2.30

Example 4 A photographic gelatin-silver chlorobromoiodide emulsion having high internal sensitivity and low surface sensitivity was prepared by the procedure described in Davey et al., U.S. Patent 2,592,250, issued April 8, 1952. The emulsion was separated into several portions and various color couplers and the hydrazide, 1-[2-(2-4-di-t-amylphenoxy)-5-(3,5-disulfobenzoamido)benzoyl] 2 phenylhydrazide, were added to the emulsion portions. For determining the eiTect of the hydrazide addendum, emulsion portions containing no hydrazide were also prepared. Each emulsion portion was coated on a cellulose acetate support at a coverage of mg. of silver, 200 mg. of gelatin, 100 mg. of coupler and 5 mg. of the hydrazide per sq. ft. The resulting color films were then exposed on an intensity scale sensitometer as described in Example 1, processed by dipping for 5 seconds with a mordanted receiving sheet in Developer D described below and then pressed into contact with receiving sheets for periods of 4 minutes at about 20 C. Thereafter the receiving sheet was removed and the dye density of the positive image on the receiving sheet determined. The improved dye densities resulting from the hydrazide emulsion addendum are summarized by the data set out in Table D below.

15 16 TABLE D sities resultipg from the hydrazide developer addendum are summarized by the data set out in Table G below.

Hydrazide Coupler Dmax TABLE G Cyan-Forming 2 0.70 Hydrazide in Coupler mnx Z 1. 96 Developer lllaggut a-Forming 3. 0

Yellow-Forming 0.92 None Cyan-forming 2 0 4 2. 74 do. 1.50

None. illaggnga-torming 2 l 4 l 1-Yfiflgdi-t(iamylphenoxy)-5-(3,fi-disull'obenzamido)beuzoyll-Q- 1O 65123. Yellgsv formingk ieu 1 r Z1 I p 2 Lliyd iox yt-$3-n-octadecylcarbamylphenylthio)-N-ethyl-3,5- o dicarboxy-Q-naphthanilide.

3 1-(4sulfophenyl)-3-(4 sulfoaniliue)-4-(2-hydroxy-l-pentadecylphenyl- 1-phenylsulfonyl-Z-phenylhydrazide. l l l lpheuylthio) 4 sulfoacetanilide 2 Same couplers as in Example 4, see Table D 01- ivay-aa y y Y I potassium salt. The data set out in Table G points up the fact that the As can be observed from the data set out in Table D, the ubject nitr g Compounds e fl ll i i hydrazide substantially increased the dye densities of the h 1n the C0101 developer as as In t e 1e t cyan, magenta, and yellow images. When conventional lhve elementsurface sensitive emulsions were substituted for the in- 2 DEVELOPER E ternal image emulsions and processed as described, there 0 G, was a complete fogging of the color films. S di lfit 0.5

DEVELOPER D 6-nitro benzimidazole Ethylene bis(pyridinium) perchlorate 0.5 Sodium lfit 5 Sodium hydroxide 6min, benzimidazole 5 4-an1ii1o-N-ethyl-N-(Q-hYdrOXYcIhY )am Ethylene bis (pyridinium)perchlorate 0.5 Water to make one hter- Sodium hydroxide 1 Exa nplg 7 4-amino-N-ethyl-N-(fl-hydroxyethyl)ani ine Polyethylene glycol (Carbowax 1540) L0 Several multicolor photographic elements were prepared by coating on cellulose acetate reflection print supports Water to make one liter.

the following layers numbered in sequence from the Example 5 support;

A film was P e as described in Example 4 (1) An emulsion optically sensitized to red light-containeohtalhlhg the eyah'fomhhg coupler, Y ing silver chlorobromoiodide at a coverage of 50 mg. A' Y P Y) P h at a of silver per square foot, gelatin at a coverage of 200 erege 50 P e the hydrezlde, mg. per square foot, and a dispersion of the cyan'form- Y P Y dlsulfohehzamldo)benzoyl] 2 ing coupler, 2-(o-diamylphenoxy-n-butyrylamino-4,6-diphenylhsfdrazldez a coverage of 5 P A chloro-S-methylphenol, in the solvent, di-n-butyl phthaltest portion of similar color film was also prepared with- 40 ate, at a Coverage f 100 135 Square f t f out the hlfdrazlde addehde for Purposes of companelcm' pler and a coverage of 50 mg. per square foot of solvent; The resulting color films were then processed as described (2) Gelatin at a Coverage of 100 per Square f t and in Example 4. The cyan-forming c up utilized was the the antistain agent, di-isooctyl hydroquinone, at a covertypethat does not form a ditfusible dye and, hence a age of 15 mg Per Square foot; positive color image was not transferred to the receiving (3) An emulsion optically sensitized to green lj hp sheet- The fe reversel lmage wes theh e taining silver chlorobromoiodide at a coverage of 100 hypo and bleached in potassium ferricyan de solution in mg of Silver per Square foot gelatin at a coverage of the usual manner. The transmission dens ties of the cyan 300 per square foot, and a dispersion of the images of the tIEIISPHI'CHCIQS prepared with and without genta forming Coupler 1 (2,4,64riCh1O1-Opheny1) 3 {3 the hydrazide in the emulsions were determ ned with a [a 2,4 (di t amylphenoxy)acetamidmbenzoamido} densitometer, the results of such are summarized by the pyrazolone, in the Solvent, 1 phosphate, at a date Set out 111 Table F belowcoverage of 150 mg. per square foot of coupler and a TABLE F coverage of 150 mg. per square foot of solvent; HYdIaZIdeI Cyan max (4) Gelatin at a coverage of 100 mg. per square foot, di-

None 033 isooctyl hydroquinone at a coverage of 15 mg. per 1 Y P Y)' i square foot, and Carey Lea silver at a coverage of benzamido)benzoyl]-2-phenylhydrazide 1.80 20 mg per Square f t Example 6 The silver chlorobromoiodide utilized in layers 1 and 3 Photographic films were prepared as described in Ex- (e e of the internal image YPe having high internal ample 4 except that no hydrazides were incorporated in slhvlty and w surface sehslhvlty and P p y the the emulsions Th6 cyamforming, magenta fonning and procedure described in Davey et al., US. Patent 2,592,250, yellow-forming couplers of Example 4 were incorporated Issued Apnl 5 The hhhs W then exposed 115mg individually in the prepared single color films. The reneutral density p tablet in an Eastman 1B 8611- sulting color films were exposed on an intensity scale seneltometer and Processed as follows: sitometer as described in Example 1. The exposed films Process Step; Time at were then processed by dipping for 5 seconds with mor- Develop min 5 danted receiving sheets in Developer E described below Rinse "min" 1 and then pressed into contact with the receiving sheets Fix "min" 2 for periods of 4 minutes at about 68 Each of the 70 Wash "min" 2 color fi.rns were developed with and without 0.3 g. per Bleach "min" 2 liter of developer of 1-pheriylsulfonyl-2-phenylhydraz1de Rinse .sec 30 11'], the developer. Thereafter the receiving sheet was Fix min 2 removed and the dye density of the positive image on the Wash min 5 receiving sheets determined. The increased dye den- Dry.

TAB LE H Cyan Magenta max Developer Cyan Dmiu Magenta min Developer F (Control) Developer G Developer H The data in Table H further illustrates the increased color density that results when the subject hydrazides are incorporated in color developers. Also, this data illustrates the desirable low densities in the D areas that result. The following processing compositions were utilized.

DEVELOPER F 4-amino-Nethyl-3-methyl-N-13 methylsultonamidoethylaniline g 10.0 Benzyl alcohol ml 10.0 Sodium sulfite 2.0 Trisodiurn phosphate 40.0 Sodium hydroxide 5.0 6-nitrobenzimidazole 0.05 Water to make one liter.

Fix

Potassium alum g Boric acid g 7.5 Acetic acid (28%) cc 40.0 Sodium thiosulfate g 240.0 Sodium sulfite (desiccated) g 15.0 Water to make one liter.

Bleach G. Potassium ferricyanide 50 Potassium bromide 20 Water to make one liter.

Example 8 Multilayer photographic elements suitable for use in preparing three-color diffusion transfer images were prepared by coating on cellulose acetate film supports the following layers numbered in sequence from the support (see FIG. 2 of the drawings):

(1) An emulsion optically sensitized to red light-containing silver chlorobromoiodide at a coverage of 135 mg. of silver per square foot, gelatin at a coverage of 250 mg. per square foot, 1-hydroxy-4-(3-n-octadecylcarbamylphenylthio)-N-ethyl-3',5 dicarboxy-2-naphthanilide 1 at a coverage of 55 mg. per square foot, and 2,5-dihydroxy-4-octadecylbenzene sulfonic acid potassium salt at a coverage of 4.5 mg. per square foot;

(2) Gelatin at a coverage of 100 mg. per square foot,

1-hydroxy-N-[5-2,4-di-t-arnylphenoxy)butyl] 2-naphthamide at a coverage of 45 mg. per square foot, and 1-hydroXy-4-(4-t-butylphenoxy) 4-phenylazo-2-naphthanilide at a coverage of 15 mg. per square foot;

(3) An emulsion optically sensitized to green light containing silver chlorobromoiodide at a coverage of 80 mg. of silver per square foot, gelatin at a coverage of 113 mg. per square foot, 1-(4-sulfophenyl)-3-(4-sulfoanaline) 4 (2 hydroxy 4-pentadecylphenylazo)- S-pyrazolone dipotassium salt at a coverage of 50 mg. per square foot, and 2,5-dihydroxy 4 octadecylbenzene sulfonic acid potassium salt at a coverage of 4.4 mg. per square foot;

(4) Gelatin at a coverage of mg. per square foot, Carey Lea silver at a coverage of 15 mg. per square foot, and 1 hydroxy N [6 (2,4 di t amylphenoxy)butyl] 2 naphthamide at a coverage of 45 mg. per square foot;

(5 An emulsion optically sensitized to blue light containing silver chlorobromoiodide at a coverage of 100 mg. of silver per square foot, gelatin at a coverage of 100 mg. per square foot, on pivalyl a (Ii-octadecylcarbamylphenylthio) 4 sulfoacetanilide potassium salt at a coverage of 100 mg. per square foot, and 2,5- dihydroxy 4 octadecylbenzene sulfonic acid potassium salt at a coverage of 3.3 mg. per square foot; and

(6) A gelatin overcoat at a coverage of 50 mg. per

square foot.

The silver chlorobromoiodide utilized in layers 1, 3 and 5 was of the internal image type having high internal sensitivity and low surface sensitivity and prepared by the procedure described in Davey et al., US. Patent 2,592,- 250, issued April 8, 1952. A similar multilayer photographic element as described above was prepared except that the hydrazide, 1-[2 (2,4 di t amylphenoxy)- 5 (3,5 disultobenzamid0)benzoyl] 2 phenylhydrazide, was utilized in layers 1, 3 and 5 of the element at coverages of 5.0 mg. per square foot in each of such layers. The prepared photographic elements were then exposed in an intensity scale sensitometer as described in Example 1 and developed in Developer I below.

DEVELOPERI G. Piperidino hexose reductone 0.80 6-nitrobenzimidazole 0.05 Sodium hydroxide 16.00 p-Aminoethyl-fl-hydroxyaniline 20.00

Water to make one liter.

The :processing of the multilayer photographic elements was carried out by immersing for 20 seconds at 68 F. the elements and photographic image receiving sheets containing the cationic mordant, dimethyl-fl-hydroxyethylu-(octadecylamido)-propyl ammonium dihydrogen phosphate, bringing the photographic elements and receiving sheets in intimate contact for 5 minutes, and then separating the photographic element and the receiving sheet to produce a positive full-color image on the receiving sheet. The increased values of the color D (measured on a Kodak Model 31A Densitometer) on the receiving sheet resulting trom the use of the hydrazide in the lightsensitive emulsions are summarized by the data set out in Table I below.

The hydrazide emulsion addenda used in this example was prepared by the following procedure. To a solution prepared from 27 g. of phenylhydrazine, 21 g. of sodium acetate, and 1 liter of glacial acetic acid was added 102 g. of 2-(2,4-ditertiary amylphenoxy) 5 nitrobenzoyl chloride (see procedure for compound 6, US. Patent 2,511,231) dissolved in 500 ml. of glacial acetic acid. The resultant mixture was stirred for one-half hour, then filtered. The filtrate was poured into 4 liters of water yielding a brown solid. The product was dried and crystallized from ligroin yielding 70 g. of tan solid, 1-[2-2,4- ditertiary amylphenoxy) 5 nitrobenzoyl] 2 phenylhydrazide, melting at 131 to 134 C. This material was 19 reduced by dissolving 70 g. in 500 ml. of ethyl acetate, adding 2 g. of 10 percent palladium on charcoal, and treating with hydrogen under three atmospheres pressure. The solvent was removed in vacuo yielding 65 g. of product, 1 [2 (2,4 ditertiary amylphenoxy) 5- aminobenzoyl] 2 phenylhydrazide, melting at 157 to 159 C. This material was acylated with 45 g. of 3,5- dichlorosulfonylbenzoyl chloride (disclosed in U.S. Patent 2,511,231) by refluxing in 1 liter of dry acetonitrile for two hours. Acetonitrile was removed in vacuo yielding a light brown solid. The latter was crystallized from ligroinbenzene yielding 57 g. of 1-[2-2,4-ditertiary amylphenoxy) 5 (3,5 dichlorosulfonylbenzamido) benzoyl]-2-phenylhydrazide. The latter was refluxed for two hours in 500 m1. of methanol containing 6 g. of sodium acetate. Methanol was evaporated yielding a tan solid which was then triturated with ethanol. The solid was collected and dissolved in 500 ml. of 75 percent aqueous methanol, and the solution was made acidic with hydrochloric acid. The precipitate which formed was dried and triturated with methanol yielding 20 g. of product, 1-[2-(2,4 ditertiary amylphenoxy 5 (3,5- disulfobenzamido) benzoyl] -2-phenylhydrazide.

Example 9 Multilayer photographic elements as described in Example 8 were processed in the presence of several hydrazides in the developer in lieu of their use in the lightsensitive emulsions. The photographic elements were then processed as described in Example 8 and positive full-color images transferred to the receiving sheet except that Developer J below was used as the developer.

DEVELOPER J G. 4-amino-N-ethyl-N-(fi-hydroxyethyl)aniline 20 Sodium sulfite 2 Sodium hydroxide 15 Water to make one liter.

The D and the D for the transferred dyes were determined as described in Example 8 and are summarized by the data set out in Table I and K below. The amounts of hydrazide indicated in the tables refer to the amount added per liter of Developer I.

TABLE J Dmin of Transferred Dye Hydrazide Red Green Blue None 0. 04 0. 07 0. 25 l-benzoyl-2-phenylhydrazide (0.30 g.) 0.09 0.06 0.19 1-acetyl-2-pheny1hydrazide (0.21 g.) 0.09 0.13 0.29 1-acetyl-2-(4-aminophenyl)hydrazide (0.23 g.) 0.06 0.10 0. 40 l-acetyl-2-(4-acetamidophenyl) hydrazide (0.30 g.) 0. 03 0. 06 0.21 l-acetyl-Z-(-pheuylsulfonamidophenyl) hydrazide (0.43 g.) 0.05 0.09 0. 32

TABLE K Dmnx of Transferred Dye Hydrazide Red Green Blue None 0. 18 0.12 0. 20 1-benzoyl-2-phenylhydrazide (0.30 g.) 0. 94 1.32 l. 31 l-acetyl-2-phenylhydrazide (0.21 g.) 0.99 1. 34 1.32 1-acetyl-2-(4-aminophenyl)hydrazide .23 g. 1.00 1. 37 1. 34 1-acetyl-2-(4-aeetamidophenyl) hydrazide (0.30 g.) 0. 92 1. 31 1. 38 l-acetyl-2-(4-phenylsulfonamidophenyl) hydrazide (0.43 g.) 0. 96 1. 11 1. 25

Example A multilayer photographic element as described in Example 8 containing 1 acetyl 2-{4[2,4-di-t-amylphe- 20 noxy) 5 (3,5 di-sulfobenzamido)benzamide]phenyl} hydrazide dipotassium salt monohydrate at a coverage of 3.5 mg. per square foot in each of layers 1, 3 and 5 was prepared. A similar photographic element was prepared for purposes of comparison without the hydrazide emulsion. The photographic elements were processed and color images transferred to receiving sheets by the general method described in Example 8. The processing cycle comprised a 10 second dip of the photographic elements and the receiving sheets in Developer K below bringing the photographic elements and receiving sheets in intimate contact for 5 minutes at E, and then separating the photographic elements from the receiving sheets to exhibit positive full-color images on the receiving sheets. The increased value of the color D resulting from the coating containing the hydrazide is pointed-up by the data summarized in Table L below.

Example 11 Multilayer photographic elements as described in Example 8 were processed in the presence of several hydrazones in gelatin top-coats on the receiving sheets used to receive the color images. The hydrazones were prepared by reacting the hydrazine, p-(fi-methylsulfonamidoethyl)phenyl hydrazine, with various aldehydes. More specifically, to ml. of 2.5% gelatin solution was added 100 mg. of p-(fi-methylsulfonamidoethyl)phenyl hydrazine. To this solution was added 2.5 ml. oxyguar gum solution (0.35% aldehyde). The resulting hydrazone-containing solution was then coated on a mordanted receiving sheet as described in Example 8 at a coverage of 100 mg. of gelatin per square foot and 10 mg. of hydrazine (as a hydrazone) per square foot. Similarly, other hydrazones were prepared by substituting 2.5 ml., 5.0 ml. and 10.0 ml. portions of formalin, as well as sufiicient mucochloric acid and benzaldehyde to react the hydrazine, for the oxyguar gum. The various hydrazones used as described below for purposes of reference in Tables M and N below.

Compound I, the hydrazine+oxyguar gum.

Compound 11, the hydrazine+formaldehyde (2.5 ml.). Compound III, the hydrazine-f-formaldehyde (5 .0 ml.). Compound IV, the hydrazine-i-formaldehyde (10.0 ml.). Compound V, the hydrazine+mucochloric acid. Compound VI, the hydrazine-i-benzaldehyde.

The photographic elements were exposed in an intensity scale sensitometer as described in Example 1, immersed in Developer L described below for about 10 seconds at about 70 F. with the hydrazone-containing receiving sheet, and thereafter the photographic elements and the receiving sheets were brought into intimate contact for 5 minutes at about 70 F. The receiving sheets and the photographic elements were then separated to yield positive full-color images on the receiving sheets. For purpose of comparison, the process was carried out without a hydrazone in the receiving sheet. The increased values of the color D on the receiving sheets resulting from the use of the hydrazones in the receiving sheet are summarized by the data set out in Table M below. Similar results are obtained when hydrazones are utilized in the light-sensitive emulsions of the photographic element.

TABLE M am: of Dxnux min of Transferred Dye Transferred Dye Hydrazone Red Green Blue Red Green Blue None (Cnt10l) 1.67 1.68 0.76 1.49 1.52 0.57 Compoundl 1.97 2.34 1.96 1.79 2.13 1.56 CompoundV 1.98 2. 54 2.35 1.79 2.22 1.95

None (Control) 1.55 1.74 1.02 1.67 1.56 0.76 Compound 11 1.82 1.81 1.54 1.64 1.63 1.24 Compound III 1.80 1.86 1.66 1.63 1.67 1.35 Compound Iv 1.92 2.18 1.97 1.75 1.98 1.65 Compound VI 1.80 2.07 2.17 1.65 1.89 1.89

DEVELOPER L Sodium hydroxide g 15.0 Ethylene bis (pyridinium)perchlorate g 1.0 fi-nitrobenzimidazole mg 60.0 Dimethylamino hexose reductone g 0.10 -(3,4-dimethoxyphenyl)-3-hydroxy tetronimide g 0.05 p-Aminoethyl-fi-hydroxy-ethylaniline g 20.0 Water to make 1 liter.

Example 12 The process of Example 11 was repeated except that oxalyl esters of phenylhydrazine in carboxymethyl cellulose topcoats were used in lieu of the hydrazones in gelatin topcoats for the receiving sheets. Receiving sheets containing topcoatings of phenylhydrazine oxalyl ethyl ester (Compound VH) in carboxmethyl cellulose and ptoluhydrazine oxalyl ethyl ester (Compound V111) in carboxymethyl cellulose at coverages of 5 mg. of the ester and 250 mg. of the carboxymethyl cellulose per square foot. The photographic elements were exposed and processed as described in Example 11 except that Developer M below was used as the developer. The improved color densities of the dyes on the receiving sheets are summarized by the data set out in Table N below.

Water to make one liter.

Example 13 The etfect of a sulfonated hydroquinone in a photographic element is illustrated by this example. Two multilayer color photographic elements of the type described in Example 8 containing the hydrazide in each of the silver halide emulsion layers were prepared except that the sulfonated hydroquinone, 2,5-dihydroxy-4-octadecylbenzene sulfonic acid potassium salt, was omitted from one photographic element and was utilized in the three silver halide emulsion layers of the other at a coverage of 1.0 mg. per square foot. The coatings were exposed and processed as described in Example 8. The

TAB LE 0 Dam of Transferred Dye Sulfouated Hydroquinone Red Green Blue Absent Present Example 14 This example illustrates that the addition of a sulfonated hydroquinone to a photographic element not containing a feature hydrazide or hydrazone of the invention imparts little or no improvement to the D of the transferred color image, particularly in the red and green. A series of multilayer photographic elements of the type described in Example 8 were prepared, except that the hydrazide was omitted from each silver halide emulsion layer and the sulfonated hydroquinone, 2,5-dihydroxy-4- octadecyl-benzene sulfonic acid potassium salt, was utilized in various concentrations in each of such emulsion layers. The photographic elements were exposed and processed as described in Example 10. The D of the transferred positive dye images for the various concentrations of sulfonated hydroquinone are set out in Table P below.

TABLE P Din of Transferred Dye Red Green Blue The data set out in Examples 13 and 14 illustrate the cooperating or synergistic elfect of the feature hydrazides or hydrazones and the sulfonated hydroquinones in the photographic elements of the invention.

Example 15 This example illustrates the advantages of utilizing a sulfonated hydroquinone in a photographic element of the invention containing a hydrazide and a nondiflusible coupler that forms a nonditfusible dye. A multicolor photographic element was prepared by coating on a polyethylene-coated paper support the following layers numbered in sequence from the support:

( 1) An emulsion sensitized to red light containing silver bromoiodide at a coverage of 38 mg. of silver per square foot, gelatin at a coverage of 200 mg. per square foot, a dispersion of a cyan dye-forming coupler of the type described in Salminen et al., US. Patent 2,423,730, issued July 8, 1947, in the solvent, di-nbutyl phthalate, at a coverage of 29 mg. per square foot of coupler and 15 mg. per square foot of solvent, 2-(2-octadecyl)-5-(2-sulfo-tert.-butyl)hydroquinone at a coverage of 4 mg. per square foot and l-formyl- 2- phenylhydrazide at a coverage of 7 mg. per square foot.

(2) Gelatin at a coverage of mg. per square foot.

(3) An emulsion sensitized to green light containing silver bromoiodide at a coverage of 75 mg. of silver per square foot, gelatin at a coverage of 300 mg. per square foot, a dispersion of a magenta dye-forming coupler of the type described in Bush et al., US. Patent 2,908,573, issued October 13, 1959 (e.g., Compounds 6-9), in the solvent, tri-o-cresyl phosphate, at a coverage of 75 mg. per square foot of coupler and 75 mg. per square foot of solvent, 2-(2-octadecyl) -5-(2-sulfo-tert.-butyl)hydroquinone at a coverage of 4 mg. per square foot and 1- 23 formyl-Z-phenylhydrazide at a coverage of 7 mg. per square foot.

(4) Yellow colloidal silver in gelatin coated at a coverage of mg. per square foot of silver and 100 mg. per square foot of gelatin.

(5) An emulsion containing blue-sensitive silver bromoiodide at a coverage of 75 mg. of silver per square foot, gelatin at a coverage of 300 mg. per square foot, a dispersion of a yellow dye-forming coupler of the type described in French Patent 1,291,110, issued March 12, 1962, in the solvent, di-n-butyl phthalate, at a coverage of 95 mg. per square foot of coupler and 48 mg. per square foot of solvent, 2-(2-octadecyl)-5-(2-sulfotert.-butyl)hydroquinone at a coverage of 4 mg. per square foot and 1-formyl-2-phenylhydrazide at a coverage of 7 mg. per square foot.

(6) Gelatin at a coverage of 100 mg. per square foot.

A photographic element of the type described above was prepared except the sulfonated hydroquinone, 2-(2-octadecyl)-5-(2-sulfo-tert.-buty1)hydroquinone was omitted from the silver halide emulsion layers. The photographic elements were then exposed in an intensity scale Eastman Ib sensitometer as described in Example 1 and processed as follows:

The D values of the resulting positive color images on the polyethylene-coated paper supports are set out in Table Q below.

TABLE Q Dmnx 0f Dye Images Sultanated Hydroquinoue Red Green Blue Absent 1. 01 0. 90 0. 90 Present 1.85 1. 96 1.86

Similar results are obtained when the following hydrazides are substituted in the same amounts for the l-formyl-Z- phenylhydrazide in each of the three silver halide emulsion layers of the photographic elements:

Substantially no dye image is obtained when the hydra- .zide is omitted. The following processing compositions were utilized to prepare the positive color images.

DEVELOPER N 4-amino-N-ethyl-3 -methyl-N-fi-methylsulfonamido ethyl aniline g 8.0 Benzyl alcohol cc 6.0 Sodium sulfite g 5.0 Trisodium phosphate g 40.0 Potassium bromide g 0.5 1% 6-nitrobenzimidazole in ethanol cc 3.0

Water to make one liter.

Another bleach-fix bath that can be suitably utilized has the following composition:

G. Sulfuric acid (conc.) 7.52 Ferric chloride hexahydrate 12.0 Ethylenediaminetetraacetic acid sodium salt 55.0 Sodium sulfite 50.0

Sodium thiosulfate pentahydrate 150.0 Ammonium thiocyanate 10.0 3,6-dithia-1,8-octanediol 10.0 Water to make one liter.

Example 16 Nonsulfonated hydroquinones do not cooperate with hydrazides and hydrazones in the processing of the photographic elements of the invention as do the feature sulfonated hydroquinones, such being illustated in this example. Two photographic elements were prepared as described in Example 15 except that in each of the silver halide emulsion layers either the sulfonated hydroquinone, 2-(2-octadecyl)-5-(2-sulfo-tert. butyl)hydroquinone, or the nonsulfonated hydroquinone, 2,5-(di-iso-octyl)hydroquinone, were utilized at a coverage of 7 mg. per square foot. The photographic elements were exposed as described in Example 15 and processed as follows:

Process step F.): Time, min. Develop (Developer 0) 6 First fix 3 Wash 3 Bleach 3 Wash 11 Second fix 3 Wash 5 Butfer 2 The D values of the resulting positive color images are set out in Table R below.

TABLE R Dam of D e Ima es Type of Incorporated y g Hydroquinone Red Green Blue Nonsulfonated 2. 05 1. 45 1. 40 Sulfonated 2. 25 2. 20 1. 96

The following processing compositions were utilized to prepare the positive color images.

DEVELOPER 0 (Same as Developer N of Example 15 plus 15 mg. per liter of p-methyl sulfonamide ethyl phenyl hydrazine.)

, 2-phenylhydrazide.

First Fix Sodium thiosulfate g 71.20 Sodium bisulfite g 11.85 Ammonium alum g 23.75 Sodium acetate -g 14.25 Boric acid g 4.76 Sodium citrate g 1.71 Water liter 1 pH 4.3.

Bleach Sodium nitrate g 28.50 Potassium ferricyanide g 16.80 Potassium bromide g 5.47 Boric acid g 2.75 Boric anhydride g 1.54 Borax (pentahydrate) g 3.33 Water liter 1 pH 7.4.

Second Fix Sodium hexametaphosphate g 1.0 Sodium sulfite g 2.5 Sodium thiosulfate pentahydrate g 100.0 Sodium carbonate-H O g 20.0 Sodium bicarbonate g 13.2 Formalin ml 20.0 Water liter 1 pH 9.5.

Buffer Citric acid g 10.79 Sodium citrate 2 6.00 Boric anhydride g 5.37 Sodium benzoate g 0.50 Zinc sulfate g 5.00 Water liter 1 pH 3.0.

Example 1 7 The photographic elements of the invention can be utilized to make color proofs from silver half-tone separation positives by successively transferring in register onto a receiving sheet a plurality of dye images as described in this example. Three single-color photographic elements or matrices (i.e., a yellow dye-forming matrix, a magenta dye-forming matrix and a cyan dye-forming matrix) were prepared, each comprising a polyethylene coated paper support having coated thereon a photographic silver halide emulsion layer corresponding to layers 1, 3 and 5 respectively of the photographic element described in Example 8, except that the silver chlorobromoiodide was coated at a coverage of 60 mg. of silver per square foot, the gelatin was coated at a coverage of 100 mg. per square foot and the hydrazide was l-formyl- The yellow matrix was exposed through a blue separation positive, the magenta matrix was exposed through a green separation positive and the cyan matrix was exposed through a red separation posi-' tive. Each of the exposed matrices were separately dipped .with a receiving sheet of the type described in Example 8 in Color Developer P described below for 15 seconds and then sandwiched together for 60 seconds at 75 F. with the receiving sheet to succesively transfer in register to the receiving sheet yellow, magenta and cyan images. Similar photographic elements or matrices were prepared as described above, except the feature hydrazide of the invention, 1-formyl-2-phenylhydrazide, was omitted from the emulsion layers for purposes of comparison. Table S below summarizes the D values for each of the separated dye images sequentially transferred in register to the same receiving sheet, both with and without the hydrazide incorporatedin the respective emulsion layers.

TABLE S Incorporated Dm; of

Photographic Element Hydrazide Transferred Dye Yellow matrir Absent 0. 1 o Present 1.5 Magenta matrix A hsent 0. 1 D0 Present 1.5 Cyan matrix- Absent 0. 1 Do Present 1.5

DEVELOPER P G. 4-amino-N-ethyl-N- (,B-hydroxy-ethyl) aniline 10.0 Sodium hydroxide 10.0 Potassium bromide 5.0 Piperidino hexose reductone 0.2

The present invention thus provides new processes in the color photographic art and new photographic elements useful in such processes.

The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim:

1. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, a nondifiusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline developing composition integral with and contiguous to said silver halide, and a nitrogen-containing compound on the silver halide emulsion side of said photographic element having a formula selected from the group consisting of (1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and

(3) R is an alkylidene radical.

2. A photographic element as described in claim 1 wherein a hydroquinone compound containing at least one sulfonic acid radical is positioned on the emulsion layer side of the photographic element.

3. A photographic element as described in claim 1 wherein the coupler is a nondiifusible coupler capable of forming a nonditfusible dye with the development oxidation product of the color developing agent.

4. A photographic element as described in claim 1 wherein the coupler is a nondifiusible coupler capable of forming a difiusible dye with the development oxidation product of the color developing agent.

5. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, a nondiifusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition integral with and contiguous to said silver halide, said coupler being selected from the group consisting of a 5- pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound on the silver halide emulsion side of said photographic element having the formula RNHNHR wherein R is an aryl radical and R is selected from the group consisting of an acyl radical and a sulfonyl radical.

6. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition integral with and contiguous to said silver halide, said coupler being selected from the group consisting of a 5- pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound on the silver halide emulsion side of said photographic element having the formula wherein R is an aryl radical and R is an alkylidene radical.

7. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, and incorporated in said emulsion layer a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition, said coupler being selected from the group consisting of a 5-pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound having the formula RNHNHi JR wherein R is an aryl radical and R is an alkyl radical.

8. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, and incorporated in said emulsion layer a nondiifusible photographic color coupled capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition, said coupler being selected from the group consisting of a 5-pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound having the formula 00 II [I wherein R is an aryl radical and R is an alkyl radical.

9. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, and incorporated in said emulsion layer a nondifiusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition, said coupler being selected from the group consisting of a 5- pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound having the formula wherein R is an aryl radical.

10. A photographic element containing a direct positive silve halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, and incorporated in said emulsion layer a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition, said coupler being selected from the group consisting of a 5- pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing com pound having the formula RNHNHC-R wherein R is an aryl radical.

11. A photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains,'and incorporated in said emulsion layer a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline color developing composition, said coupler being selected from the group consisting of a 5- pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, and a nitrogen-containing compound having the formula wherein R is a phenyl radical.

12. A photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-phenylacetyl-Z-phenyhydrazide.

13. A photographic element as described in claim 11 wherein the nitrogen-containing compound is l-formyl-Z- phenylhydrazide.

14. A photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-lauroyl-2- phenylhydrazide.

15. A photographic element as described in claim 7 wherein the nitrogen-containing compound is 1-acetyl-2- {4 [2 (2,4 ditertiaryamylphenoxy) 5 (3,5 disulf obenzamido benzamido phenyl} hydrazide.

16. A photographic element as described in claim 10 wherein the nitrogen-containing compound is 1-[2-(2,4- ditertiaryamylphenoxy) 5 (3,5 disulfobenzamido) benzoyl] -2-phenylhydrazide.

17. A light-sensitive photographic element comprising a support with superposed red, green and blue light-sensi tive direct positive silver halide emulsion layers wherein the silver halide forms latent images predominantly inside the silver halide grains, integral with said element and contiguous to said emulsion layers, respectively, a cyan dye-forming coupler, a magenta dye-forming coupler and a yellow dye-forming coupler, and a nitrogen-containmg compound having a formula selected from the group consisting of (1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and

(3) R is an alkylidene radical;

said couplers being nondiffusible during development in an alkaline color developing composition containing an aromatic primary amino color developing agent, capable of forming diffusible acid dyes in said alkaline color developing composition by reaction with oxidation product of said color developing agent and having a formula selected from the group consisting of DYELINK COUP-BALL) n and BALL LINK (COUPSOL) wherein:

(l) DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;

(2) LINK is a connecting radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical and a dithio radical;

( 3) COUP is a coupler radical selected from the group consisting of a S-pyrazolone coupler radical, a'phenolic coupler radical, and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;

(4) BALL is a photographically inert organic ballasting radical having at least 8 carbon atoms and of such molecular size and configuration as to render said couplers nondilfusible during development in said alkaline color developing solution;

() SOL is selected from the group consisting of a hydrogen atom and an acidic solubiliziug group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubiliziug group when said color developing agent is free of an acidic solubiliziug group; and

(6) n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, monothio radical, and dithio radical.

I R1 GR SOaH and (1) R is selected from the group consisting of an alkyl radical, an acylamino radical, a hydrogen atom and a sulfonic acid radical,

(2) R is selected from the group consisting of an alkylene radical and an acylamino radical, and (3) R is selected from the group consisting of an alkyl radical and an acylamino radical,

wherein and a nitrogen-containing compound on the silver halide emulsion side of said photographic element having a formula selected from the group consisting of wherein:

(1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and

(3) R is an alkylidene radical.

19. A photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing a silver halide direct positive emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains and a nondiffusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and continguous to said silver halide, said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out with said developing composition in the presence of a nitrogencontaining compound having a formula selected from the group consisting of R-NHNH-R wherein:

(1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and (3) R is an alkylidene radical.

20. The process as described in claim 19 wherein the nitrogen-containing compound is positioned on the emulsion side of the photographic element.

21. The process as described in claim 19 wherein the nitrogen-containing compound is incorporated in the developing composition.

22. A process as described in claim 19 wherein the photographic element contains a hydroquinone compound containing at least one sulfonic acid radical on the emulsion side of the photographic element.

23. A photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains and a nondifiusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and continguous to said silver halide, said coupler being selected from the group consisting of a S-pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out in the presence of a nitrogen-containing compound having the formula RNHNHR wherein R is an aryl radical and R is selected from the group consisting of an acyl radical and a sulfonyl radical.

24. A photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing a silver halide direct positive emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains and a nondiffusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color devel- 'oping agent integral with said photographic element and continguous to said silver halide, said coupler being selected from the group consisting of a S-pyrazolone coupler, a phenolic coupler and an open-chain ketomethylene coupler, said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out in the presence of a nitrogen-containing compound having the formula RNI-IN=R wherein R is an aryl radical and R is an alkylidene radical.

25. A color photographic ditfusion transfer process which comprises exposing a light-sensitive photographic element comprising a support having superposed thereon red, green and blue light-sensitive direct positive silver halide emulsion layers wherein the silver halide forms latent images predominantly inside the silver halide grains, integral with said element and contiguous to said emulsion layers, respectively, a cyan dye-forming coupler, a magenta dye-forming coupler and a yellow dye-forming coupler, said couplers being nondifiusible during development in an alkaline color developing composition containing an aromatic primary amino color developing agent, capable of forming diffusible acid dyes in said alkaline color developing solution by reaction with oxidation product of said color developing agent and having a formula selected from the group consisting of DYELINK(COUP-BALL) and BALLLINK COUPSOL) wherein:

(l) DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group;

(2) LINK is a connecting radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, an alkylidene radical, a monothio radical and a dithio radical;

(3) COUP is a coupler radical selected from the group consisting of a -pyrazolone coupler radical, a phenolic coupler radical, and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;

(4) BALL is a photographically inert organic ballasting radical having at least 8 carbon atoms and of such molecular size and configuration as to render said couplers nondiffusible during development in said alkaline color developing solution;

(5) SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color developing agent is free of an acidic solubilizing group; and

(6) n is an integer of 1 to 2 when said LINK is an alkylidene radical, and n is 1 when said LINK is a radical selected from the group consisting of an azo radical, an azoxy radical, a mercuri radical, an oxy radical, a monothio radical, and a dithio radical;

wetting said element with said alkaline color developing composition and developing said emulsions, said couplers coupling with oxidation product of said color developing agent during said development and thereby cleaving said LINK in said couplers releasing diifusible acid dye images in areas of the said development, said dye images diffusing imagewise in register to a juxtapositioned reception layer containing a mordant for acid dyes and thereby producing a positive color reproduction of said subject, said developing being carried out in the presence of a nitrogen-containing compound having a formula selected from the group consisting of RNHNHR and R--NHN:R

wherein:

(1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and

(3) R is an alkylidene radical.

26. A photographic process for preparing direct positive color images which comprises color developing with an alkaline color developing composition containing an aromatic primary amino color developing agent an imageexposed photographic element containing (a) a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains, (b) a nonditfusible photographic color coupler capable of forming a dye when reacted with resulting development oxidation product of said color developing agent integral with said photographic element and contiguous to said silver halide, and (c) a sulfonated hydroquinone on the emulsion side of the photographic element having a formula selected from the group consisting of R S 0 H and wherein (1) R is selected from the group consisting of an alkyl radical, an acylamino radical, a hydrogen atom and a sulfonic acid radical,

(2) R is selected from the group consisting of an alkylene radical and an acylamino radical, and

( 3) R is selected from the group consisting of an alkyl radical and an acylamino radical,

said coupler reacting with said oxidation product to form a dye in regions of development, and said color developing being carried out with said developing composition in the presence of a nitrogen-containing compound having a formula selected from the group consisting of (1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and

(3) R is an alkylidene radical.

27. A photographic proofing process which comprises exposing a plurality of single-color photographic elements as described in claim 4 to silver image separation positives of a multicolor photographic record substantially complementary in color to the ditlusible dye formed by color developing the respective elements in an alkaline composition containing an aromatic primary amino color developing agent, successively color developing the photographic elements with said alkaline composition, and successively transferring in register resulting diffusible dyes to a juxtapositioned receiving sheet to produce a positive multicolor image on said receiving sheet' 28. A photographic process as described in claim 27 wherein the photographic elements contain a sulfonated hydroquinone on the emulsion side having a formula selected from the group consisting of OH OH R SOaH and (1) R is selected from the group consisting of an alkyl radical, an acylamino radical, a hydrogen atom and a sulfonic acid radical,

(2) R is selected from the group consisting of an alkylene radical and an acylamino radical, and

(3) R is selected from the group consisting of an alkyl radical and an acylamino radical.

29. A photographic element comprising a support having coated thereon a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains containing a nondiffusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent, 1-formyl-2-phenylhydrazide at a coverage of about 1 to 20 mg. per square foot and 2,5-dihydroxy-4-octadecylbenzene sulfonic acid at a coverage of about .1 to 10 mg. per square foot.

30. A photographic element comprising a support having coated thereon a direct positive silver halide emulsion layer wherein the silver halide forms latent images predominantly inside the silver halide grains containing a nondiifusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent, 1 [2-(2,4-di-t.-amylphenoxy)-5-(3,5-disultobenzamido)benzoyl]-2-phenylhydrazide at a coverage of about 1 to 20 mg. per square foot and 2,5-dihydroxy-4-octadecylbenzene sulfonic acid at a coverage of about .1 to 10 mg. per square foot.

31. A photographic direct positive silver halide emulsion wherein the silver halide forms latent images predominantly inside the silver halide grains, said emulsion containing a non-difiusible photographic color coupler capable of forming a dye when reacted with development oxidation product of an aromatic primary amino color developing agent in an alkaline developing composition, and a nitrogen-containing compound having a formula selected from the group consisting of wherein:

( 1) R is an aryl radical,

(2) R is selected from the group consisting of an acyl radical and a sulfonyl radical, and (3) R is an alkylidene radical.

References Cited by the Examiner UNITED STATES PATENTS 1/1943 Albers et al. 9656 8/1951 Ives 9664 5/1952 Ives 9664 2/1955 Thirtle et al. 96-56 7/1956 Yutzy 963 3/1960 Coenen et al. 96100 6/1960 Whitmore et al. 963

FOREIGN PATENTS 2/ 1959 Belgium.

NORMAN G. TORCHIN, Primary Examiner.

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Classifications
U.S. Classification430/239, 430/598, 430/226, 430/217, 430/241, 430/378, 430/218, 430/358, 430/409, 430/941, 430/236
International ClassificationG03C7/30, G03C8/12, G01C19/40, G03C5/30, G03C8/08
Cooperative ClassificationG01C19/40, G03C7/3022, G03C8/12, Y10S430/142, G03C8/08, G03C5/3014
European ClassificationG01C19/40, G03C8/12, G03C7/30L, G03C5/30D, G03C8/08